EP0203632B1 - Katalysator für die selektive Zersetzung von Cumolhydroperoxid und Verfahren zu dessen Herstellung - Google Patents

Katalysator für die selektive Zersetzung von Cumolhydroperoxid und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP0203632B1
EP0203632B1 EP86200664A EP86200664A EP0203632B1 EP 0203632 B1 EP0203632 B1 EP 0203632B1 EP 86200664 A EP86200664 A EP 86200664A EP 86200664 A EP86200664 A EP 86200664A EP 0203632 B1 EP0203632 B1 EP 0203632B1
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EP
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Prior art keywords
catalyst
silicate
temperature
crystals
sio2
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EP86200664A
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English (en)
French (fr)
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EP0203632A2 (de
EP0203632A3 (en
Inventor
Ugo Romano
Mario Gabriele Clerici
Giuseppe Bellussi
Franco Buonomo
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Enichem Sintesi SpA
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Enichem Sintesi SpA
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Priority to AT86200664T priority Critical patent/ATE65941T1/de
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Publication of EP0203632A3 publication Critical patent/EP0203632A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to a catalyst for the selective decomposition of cumene hydroperoxide into phenol and acetone, and to the use of said catalyst for that decomposition reaction.
  • cumene is peroxidated to cumene hydroperoxide, and the latter is decomposed by the agency of an acidic catalyst, which is sulphuric acid: such a procedure produces phenol and acetone, but accompanied by acetophenone and sulphonated by-products which pollute the desired products and are difficult to separate.
  • an acidic catalyst which is sulphuric acid
  • the present invention aims at carrying out the decomposition reaction in question with the aid of a catalyst other than sulphuric acid,which is a modified zeolite.
  • a catalyst other than sulphuric acid which is a modified zeolite.
  • EP-A-168 978 discloses zeolites which contain oxides of silicon, aluminium and boron: these zeolites can be used, among others, for preparing the modified zeolites to be used according to the present invention.
  • the invention therefore, provides a silicon-, aluminium- and boron-based catalyst for the selective decomposition of cumene hydroperoxide into phenol and acetone, in which silicon-, aluminium- and boron oxides form crystals having a zeolite-structure, and aluminium and boron partially replace silicon in the crystalline structure of silica, characterized in that said crystals are interconnected by oligomeric silica. It is preferred that the molar ratio of the silica of the zeolite crystals to the oligomeric silica is from 80 to 95.
  • the catalyst is one having the form of microspheres of a size of from 5 ⁇ m to 100 ⁇ m, and, preferably, from 20 ⁇ m to 100 ⁇ m.
  • the catalyst after calcination at 550°C and cooling to room temperature, has the formula: 0,017 to 0,0025 Al2O3 . 0,1 to 0,005 B2O3 - SiO2 with from 0,2 to 0,5 water .
  • the invention furthermore, provides a process for preparing the catalyst defined in claim 1, comprising:
  • the first step is accomplished by starting from alkyl silicates (alkyl groups of from 1 to 4 carbon atoms), in particular from tetramethyl- and/or tetraethylsilicate, possibly in aqueous solution which are added to an alcoholic solution (aliphatic alcohol of from 1 to 6 carbon atoms) of an aluminium salt at a concentration of preferably from 4 to 5%, preferably an alcoholic solution of Al nitrate or acetate, the whole being then mixed with an aqueous solution of tetracrocylammonium hydroxide and H3BO3 . From the reaction medium foreign cations, in particular cations of alkaline or alkaline-earth metals, must be absent.
  • alkyl silicates alkyl groups of from 1 to 4 carbon atoms
  • tetramethyl- and/or tetraethylsilicate possibly in aqueous solution which are added to an alcoholic solution (aliphatic alcohol of from 1 to 6 carbon atom
  • the whole is heated under stirring to a temperature comprised within the range of from 50 to 80°C, preferably to 60°C, to the purpose of hydrolyzing the alkyl silicate and removing an amount as high as possible of the alkyl alcohol obtained from the hydrolysis and of the alcohol outcoming from the solution of the aluminium salt.
  • the resulting residual solution is charged into an autoclave equipped with a stirrer, and is heated, under its autogenous pressure, at a temperature of 150 to 250°C, for a time period comprised within the range of from 3 hours to 10 days, a suspension of crystals being obtained.
  • the crystals of the suspension are then separated from the mother liquors, preferably by centrifuging, washed in deionized water and dried, preferably by centrifuging.
  • the second step consists in dispersing the above said zeolite crystals in a clear solution obtained by hydrolyzing a tetraalkyl silicate (alkyl group of from 1 to 4 carbon atoms), preferably tetramethyl- or tetraethyl-silicate, in an aqueous solution of tetraalkylammonium (TAA) hydroxide (alkyl group of from 1 to 5 carbon atoms) for a time comprised within the range of from 1 to 2 hours at a temperature of 60-70°C.
  • a tetraalkyl silicate alkyl group of from 1 to 4 carbon atoms
  • TAA tetraalkylammonium
  • the suspension obtained is atomized, preferably by means of a spray drier, microspheres having an average diameter comprised within the range of from 5 to 1000 ⁇ m, preferably of from 20 to 100 ⁇ m, being obtained.
  • microspheres are then calcined at a temperature of from 500 to 600°C, preferably at 550°C for 2-10 hours, preferably for 5 hours.
  • the reaction mixture for the synthesis of the zeolite has the following molar composition: 0.1-0.35 tetrapropylammonium oxide; SiO2; 0.0025-0.01 Al2O3; 0.2-0.02 B2O3; 20-40 H2O.
  • the reaction mixture for the preparation of the catalyst has the following composition by mol (with the exclusion of Al2O3 and B2O3): 0.05-0.15 tetraalkylammonium oxide; 4-19 SiO2 (of zeolite); 1 SiO2 (of tetraalkyl Silicate); 80-600 H2O.
  • a third object of the present invention is the method for the selective decomposition of cumene hydroperoxide into phenol and acetone using the above said catalyst.
  • the method according to the invention consists in contacting cumene hydroperoxide with the catalyst, preferably placed inside a reactor on one or more stationary or fluidified beds at a temperature of from 20 to 120°C, preferably of 40-60°C, and in discharging the reaction products and indecomposed cumene hydroperoxide.
  • Cumene hydroperoxide can be supplied as such, or diluted in a suitable solvent, in particular cumene.
  • the space speed LHSV referred to cumene hydroperoxide in case of continuous operating is comprised between 0.5 and 10 h ⁇ 1.
  • the permanence time is comprised within the range of from 1' min to 120' min it being preferably of 15 min. - 20 min.
  • the so-obtained solution is charged into an autoclave equipped with a stirrer and is heated under its autogenous pressure under stirring for 4 hours at 170°C.
  • the discharged product is centrifuged and the cake is accurately dispersed in 70 litres of deionized water, the obtained suspension is again centrifuged, yielding a washed cake.
  • the finished catalyst (A) is thus obtained, the chemical analysis of which is as follows: SiO2: 96.87; Al2O3: 1.851; B2O3: 1.029; H2O: balance to 100.
  • Example 2 Following the procedure as disclosed in Example 1, the washed cake discharged from the centrifuge is obtained.
  • the solid is calcined under H2 with the temperature being raised from room temperature to 550°C and then at a constant temperature of 550°C in air for 4 hours.
  • the product obtained (B) has the following chemical composition: SiO2: 96.93; Al2O3: 1.968; B2O3: 0.852; H2O: balance to 100.
  • the discharged milky suspension is centrifuged, the cake is dispersed in 500 g of deionized water and the suspension is centrifuged.
  • the washed cake is then calcined by increasing the temperature, over a 1h and 30min. time, under N2, from room temperature to 550°C and then at a constant temperature of 550°C in air for 4 hours.
  • the product obtained (C) has the following composition: SiO2: 96.58; Al2O3: 1.077; H2O: balance to 100.
  • the discharged milky suspension is centrifuged, the cake is dispersed in 500 g of deionized water and the suspension is centrifuged.
  • the washed cake is then calcined by increasing the temperature, over a 1h and 30 min. time, under N2, from room temperature to 550°C and then at a constant temperature of 550°C in air for 4 hours.
  • the produce obtained (D) has the following composition: SiO2: 97.55; B2O3: 1.954; H2O: H2O: balance to 100.
  • the decomposition of cumene hydroperoxide is carried out by using, in lieu of the 3 g of catalyst A, 0.2 g of catalyst E (sulphuric acid in aqueous solution at 96%) and adjusting the addition rate of CHP so that the addition takes place within a time of 10'; the temperature is kept always at 40°C. After a total time of 30 min. the reaction mixture is neutralized by sodium bicarbonate, and analyzed by iodimetric titration and gas-chromatographic analysis.
  • CHP cumene hydroperoxide
  • a test is carried out by operating in continuous by using an equipment consisting of a glass reactor of 0.5 l in volume, equipped with mechanical stirring means, automatic level control, temperature control system, inlet for the cumene hydroperoxide solution, outlet for the outflowing stream, and equipped with a filtering candle to avoid losses of catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (14)

  1. Katalysator auf der Basis von Silizium, Aluminium und Bor für die selektive Zersetzung von Cumolhydroperoxid zu Phenol und Aceton, worin Silizium-, Aluminium- und Boroxide Kristalle mit einer Zeolithstruktur ausbilden und Aluminium und Bor partiell Silizium im Kristallgitter von Siliziumdioxid ersetzen, dadurch gekennzeichnet, daß diese Kristalle durch oligomeres Siliziumdioxid miteinander verbunden sind.
  2. Katalysator nach Anspruch 1, worin das Molvehältnis des Siliziumdioxids der Zeolithkristalle zu oligomerem Siliziumdioxid von 80 bis 95 beträgt.
  3. Katalysator nach Anspruch 1 in Form von Mikrokügelchen mit einer Größe von 5 µm bis 1 .000 µm, vorzugsweise von 20 µm bis 100 µm.
  4. Katalysator nach Anspruch 1, der, nach Calcinierung bei 550°C und Abkühlen auf Raumtemperatur, die Formel:
    0,017 bis 0,0025 Al₂O₃ . 0,1 bis 0,005 B₂O₃ SiO₂ mit 0,2 bis 0,5 Wasser aufweist.
  5. Verfahren zur Herstellung des in Anspruch 1 definierten Katalysators, umfassend:
    a) eine erste Stufe der Bereitung von Zeolithkristallen, worin Aluminium und Bor Silizium in der Kristallstruktur von Siliziumdioxid ersetzen, und
    b) eine zweite Stufe, worin die solcherart erhaltenen Zeolithkristalle in einer klaren Lösung, die durch Hydrolysieren eines Tetraalkylsilikats in einer wäßrigen Tetraalkylammoniumhydroxidlösung während 1 bis 2 Stunden bei einer Temperatur von 60 bis 70°C erhalten worden ist, dispergiert werden, wonach die gebildete Suspension zur Ausbildung von Mikrokügelchen mit einem mittleren Durchmesser von 5 µm bis 1.000 µm zerstäubt wird und diese Mikrokügelchen bei einer Temperatur von 500 bis 600°C während 2 bis 10 Stunden calciniert werden.
  6. Verfahren nach Anspruch 5, worin das Tetraalkylsilicat C₁-bis C₄-Alkylgruppen aufweist.
  7. Verfahren nach Anspruch 6, worin das Tetraalkylsilicat unter Tetramethylsilicat und Tetraethylsilicat ausgewählt wird.
  8. Verfahren nach Anspruch 5, worin die Mikrokügelchen bei 550°C calciniert werden.
  9. Verfahren nach Anspruch 5, worin das Tetraalkylammoniumhydroxid C₁ - C₅-Alkylgruppen aufweist.
  10. Verfahren nach Anspruch 5, worin in der ersten Stufe Zeolithkristalle durch Zusetzen eines Alkylsilicats zu einer alkoholischen Lösung eines Aluminiumsalzes und Vermischen der gebildeten Lösung mit einer wäßrigen Lösung von Tetrapropylammoniumhydroxid und H₃BO₃, Erhitzen unter Rühren auf eine Temperatur von 50 bis 80°C zum Hydrolysieren des Alkylsilicats und Abtrennen des Alkylalkohols, der sowohl aus dieser Hydrolyse herrührt als auch aus der alkoholischen Lösung des Aluminiumsalzes stammt, und Erhitzen der verbleibenden Lösung auf eine Temperatur von 150 bis 250°C in einem Autoklaven unter ihrem autogenen Druck während einer Zeitdauer von 3 Stunden bis 10 Tagen zur Erzielung einer Suspension von Kristallen, hergestellt werden.
  11. Verfahren nach Anspruch 10, worin die Reaktanten entsprechend der folgenden molaren Zusammensetzung vermischt werden:
    - 0,1 bis 0,35 Tetrapropylammoniumhydroxid;
    - SiO₂;
    - 0,0025 bis 0,01 Al₂O₃;
    - 0,2 bis 0,02 B₂O₃, und
    - 20 bis 40 H₂O.
  12. Verfahren nach Anspruch 5, worin in der zweiten Stufe zum Verbinden der Zeolithkristalle durch oligomeres Siliziumdioxid die Reaktanten genäß der folgenden Molzusammensetzung vermischt werden:
    - 0,05 bis 0,15 Tetraalkylammoniumhydroxid;
    - 4 bis 19 SiO₂ (aus dem Zeolith);
    - 1 SiO₂ (aus dem Tetraalkylsilicat), und
    - 80 bis 600 H₂O.
  13. Verwendung des in Anspruch 1 definierten Katalysators zur selektiven Zersetzung von Cumolhydroperoxid zu Phenol und Aceton.
  14. Verwendung des Katalysators nach Anspruch 13, worin Cumolhydroperoxid bei einer Temperatur von 20 bis 120°C, vorzugsweise von 40 bis 60°C mit dem Katalysator in Kontakt gebracht wird.
EP86200664A 1985-04-23 1986-04-18 Katalysator für die selektive Zersetzung von Cumolhydroperoxid und Verfahren zu dessen Herstellung Expired - Lifetime EP0203632B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86200664T ATE65941T1 (de) 1985-04-23 1986-04-18 Katalysator fuer die selektive zersetzung von cumolhydroperoxid und verfahren zu dessen herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT20458/85A IT1187662B (it) 1985-04-23 1985-04-23 Catalizzatore per la decomposizione selettiva del cumilidroperossido e procedimento utilizzante lo stesso
IT2045885 1985-04-23

Publications (3)

Publication Number Publication Date
EP0203632A2 EP0203632A2 (de) 1986-12-03
EP0203632A3 EP0203632A3 (en) 1988-08-17
EP0203632B1 true EP0203632B1 (de) 1991-08-07

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EP86200664A Expired - Lifetime EP0203632B1 (de) 1985-04-23 1986-04-18 Katalysator für die selektive Zersetzung von Cumolhydroperoxid und Verfahren zu dessen Herstellung

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US (2) US4743573A (de)
EP (1) EP0203632B1 (de)
AT (1) ATE65941T1 (de)
DE (1) DE3680717D1 (de)
IT (1) IT1187662B (de)

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IT1213504B (it) * 1986-10-22 1989-12-20 Eniricerche Spa Zeoliti legate e procedimenye per la loro prosuzione.
US5119319A (en) * 1989-12-14 1992-06-02 Options Unlimited Research Corp. Full-duplex video communication system
US5399749A (en) * 1991-09-09 1995-03-21 Henkel Corporation Catalyzed process for oxidation of ozonides of unsaturates to carboxylic acids
US5254751A (en) 1992-09-14 1993-10-19 General Electric Company Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone
NL9201756A (nl) * 1992-10-09 1994-05-02 Univ Delft Tech Werkwijze voor de gekatalyseerde ontleding van organische hydroperoxiden.
US7230545B2 (en) * 2003-11-07 2007-06-12 Nattel Group, Inc. Automobile communication and registry system
WO2007137021A2 (en) * 2006-05-16 2007-11-29 Shell Oil Company Catalysts comprising a combination of oxidized metals and a method for cleaving phenylalkyl hydroperoxides using the catalysts
US7417003B2 (en) * 2006-12-29 2008-08-26 Uop Llc Solid acid catalyst and process for decomposition of cumene hydroperoxide
RU2560183C1 (ru) * 2014-08-08 2015-08-20 Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" Способ получения катализатора для разложения алкилароматических гидропероксидов
DE102022113953A1 (de) 2022-06-02 2023-12-07 Technische Hochschule Köln, Körperschaft des öffentlichen Rechts Verfahren zur Umlagerung von Peroxidverbindungen

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US3275571A (en) * 1962-09-11 1966-09-27 Exxon Research Engineering Co Crystalline zeolite composition and method of preparation thereof
US3328119A (en) * 1963-09-18 1967-06-27 Exxon Research Engineering Co Synthetic crystalline alumino-borosilicate zeolites and preparation thereof
US3531397A (en) * 1967-12-11 1970-09-29 Universal Oil Prod Co Method of catalyst preparation
GR66589B (de) * 1978-06-22 1981-03-30 Snam Progetti
NL7811732A (nl) * 1978-11-30 1980-06-03 Stamicarbon Werkwijze voor de omzetting van dimethylether.
US4299733A (en) * 1980-05-08 1981-11-10 Uop Inc. High octane FCC catalyst
US4427577A (en) * 1980-12-12 1984-01-24 Exxon Research & Engineering Co. Composite zeolite
JPS59120247A (ja) * 1982-12-27 1984-07-11 Idemitsu Kosan Co Ltd 新規なゼオライト触媒およびその製造方法ならびにそれを用いる方法
US4490566A (en) * 1983-05-06 1984-12-25 Mobil Oil Corporation Production of phenol
US4594332A (en) * 1983-10-20 1986-06-10 Basf Aktiengesellschaft Preparation of hard, fracture-resistant catalysts from zeolite powder
US4526880A (en) * 1984-07-16 1985-07-02 Mobil Oil Corporation Hydrothermal zeolite activation

Also Published As

Publication number Publication date
DE3680717D1 (de) 1991-09-12
US4849387A (en) 1989-07-18
US4743573A (en) 1988-05-10
ATE65941T1 (de) 1991-08-15
EP0203632A2 (de) 1986-12-03
IT1187662B (it) 1987-12-23
EP0203632A3 (en) 1988-08-17
IT8520458A0 (it) 1985-04-23

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